Amides of cyclic sulfones



Patented Jan. 27, 1948 t I 2,435,071 I if Amnas orcrcuc sULFoNEs Theodore W. Evans, Oakland. Rupert 0. Morris, Berkeley, and Edward Shokal, Oakland, Califz, asslrmors to Shell Development Come pany. .San Francisco, Calif., 'a' corporation of Delaware; I

This invention relates to a novel and useful class of compounds, and particularly pertains to the reaction products formed by "the interaction of a carboxylic acid,- or of the corresponding anhydride. with amino derivatives of cyclic sulfones. Specifically. the invention is directed to substituted and unsubstituted sulfolanylamines' and suliolenylaminesin which at-least one of the hydrogen atoms otthe" amino radical is substituted by an acyl radical.

The terms sulfolanylamine and "sulfolenylamine" refer to the mom derivatives of sulwis termed' f'thiacyclopentane 1,1 dioxide, thiolane-Ll-dloxlde," cyclote'tramethylene sul- .!cne ,'or "dlhydrobutadiene sulfone." Similarly, the-term suli'olene"]refers to an unsaturated suliolane, i e., sulfolaneicontaining a single olefin [T s r-Ares PATENT Horn I no nrswinafln pucanonsul 19, 19 43,

.lClaims. (cuss-429) linkage 'betwe'e nany two adjoining carbon atoms.

This compound as. also called iithiacyclopentene-L'l-dloxide. Thelvdouble bond may be between any two adjacent carbon atoms of the ring, the generic term suli'olenelcovering both the simple unsubstitutedv 2-sulIolene (which is 2- thiolene l,,1 -dioxlde or alpha-butadiene sulfone), and the unsubstituted 3-sulfolene (which-is 3- thiolenedA-dioxide or beta-butadiene sulione), as well as thesubstituted derivatives thereof, 1. e.. suli'olenes in which different organic and/or inorganic radicals are substituted for. one or more oi the-' hydrogen'atoms of both simple unsubstituted fsuliolenes. Similarly. the term suliolane generically covers both the unsubstituted sultolane havlng the general formula.

Bic-CE! and the substituted derivatives of this cdmpound,

other =,:objects will be apparent from thedescription oithe imrentiomv amino radical is attached tcthe,

Broadly. the amidesfan 'l iiif ds states invention comprise the reaction p1; ucts kit a substituted or unsubstituted: .suli olaiiylamlne or sulfolenylamine wlthfj a 'c'erbpxy1ic acid v or .its

'a'mid'es consist] of substituted or unsubstiflenyl amines in vyq'rsseri om ,ubstit'uted, hy,.a a I Medical, A. eferred subgroup oi the'novelj ccmpo ds prises'the reaction productsof'a caro i or 'anhydride 'with sulfolan'ylamin n whicl the is carb n-at in the 3 -posit lon, the remaining free bonds of the nuclear carbon atoms of the ,suliolane ring be,- ing taken up by hydrogen a s, .,ha l 08 p qt ms, hydroityl radicals, and/or 0' n'icradicals, prefembly, Y s a'r e dlce group 'of amides may be epresentedgby the; fol

tuted sulfolanylamines' or which at least one "oi? t lowing fieneral structuralfformula:

0 rivative thereof, e. g. halo-substituted "derivative,

while the radicals R: through Ra arefeach' a, member of the group consisting of the hyd'rogn atom,

a halogen atom, the hydroxyl radicalfjand an or-' ganic radical,'preferably a hydrocarbon radical. Examples of such hydrocarbon radicals are meth: yl, ethyl, propyl, isopropyl, n butyl, iso'butyl, secondary butyl, tertiary but'yigmormal pentyl, isopentyl, secondary peiitylfi;l exyy octyl, decyl, dodecyl, tetradecylfcetylfstearyl, trinithyloctadecyl, :allyl, methallyl, crctyl, ethyl vinyl carbinyl, butenyl, pentenyl, hexen'yl', propargyl, ally],

methallyl phenyl, naphth'yF' allyll'fphenyl vinyl carbinyl, cyclop'entyl; -cycloheryl', f'ethyl cyclohexyl, cyclopentenyl; cyclohexenyl; and vinyl cyclohexenyl. Also,-the hydrogen? atom of the imino (imido) "radical may be substituted by an organic, and preferably "a hydrocarbon, radical.

The amides and imides of the present invention may be prepared by reacting, preferably via preferred sub-1 folanylamine or of the suliolenylamine.

a condensationreaction, a carboxylic acid .or the corresponding anhydride with a cyclic sulfone containing an amino radical directly attached to one of the nuclear carbon atoms. As examples of the amino substituted cyclic sulfones which I refluxing. In some instances. the rate of reaction may thus be reacted with the carboxylic acids or their anhydrides. reference is made to 3-sulfolanylamine (ii-amino cyclotetramethylene sulfone) and 3-sulfolenylamine (3-amino-4-sulfolene). as well as other various sulfolanylamines and sulfolenylamines which contain various substituents and particularly alkyl radicals attached to the various nuclear carbon atoms. e. g. 2- methyl-3-sulfolanylamine. 2,4-dimethyl 4 sulfolanylamine. and the like .and their homologue: and analogues; I L 1 Any carboxylic acid. whether saturated or unsaturated. as well'as any carboxylic acidanhydride, may be used as the reactant in the .manufacture of the novel amides. Representative examples of the saturated carboxylic acids which may thus be employed are formic, acetic, propicnic. butyric, valeric, ca'proic, caprylic, capric, lauric, myristic, palmitic, stearic, behenlc. cerotic. and the like. The following are examples of the unsaturated carboxyiic acids which maybe employed as a reactant: acrylic, crotonic. isocro-j tonic, alpha-methyl acrylicjvinyl acetic, betaethyl acrylic. beta-vinyl acrylic. beta-beta-dimethyl acrylic, beta-pentenoic. allyl acetic. an-

gelic, tiglic. hydrosorbic, sorbic, teracrylic, myristolenic, oleic, linoleic. linolenic, maleic, fumaric. citric, citraconic, mesaconic, itaconic, glutaconic,

and the like. Also, substituted acids such as the halogenated fatty acids of the type of chloroformic. chioracetic, bromopropionic. chloracrylic. chlorocrotonic, and the like, are suitable in this reaction. Generically, the above group is intended to include allcarboxylic acids containing one or morecarboxyl groups, and in the case of unsaturated acids one or more unsaturated bonds between two carbon atoms, preferably of aliphatic character. A preferred group of acids comprises the saturated and unsaturated fatty acids. As stated, the anhydrides of the above acids, and preferably of the mentioned and other fatty acids, may be also used. As will be pointed out hereinbelow, the use of polybasic acid anhydrides generally tends to form the corresponding imides. whereas the use of the monobasic acids, unless the latter are employed in an excess, will produce the corresponding amide of the sul- The formation of the amides or imides in accordance with the present invention may be effected without resorting to the use of any catalysts, although in some cases various reaction promoters or catalysts may be employed, par ticularly when it is desired to accelerate the rate of formation of the desired amide or imide. The reaction may be effected in a wide variety of manners. For example, the reaction may be realized by a mere heating of the acid or anhydride in contact with theamino derivative of the cyclic sulfone. the reactants being preferably introduced into a suitable reaction vessel equipped with means for agitation, and heating the reactants. The reactants may be introduced into the reaction vessel independently or they may be mixed prior to their introduction thereinto. In a majority of cases, the formation of the amido or imldo derivatives is effected by heating the reactants in contact with each other at or about the boiling temperature of the reaction mixture at atmospheric pressure and with or without may be accelerated by resorting to the use of superatmospheric pressures and higher temperatures. Inorder to prevent undesirable side reactions. it is preferable to effect the reaction by operating 'in such a manner that the water formed as the result of the reaction is removed from the reaction zone substantially as soon as formed. This may be eflected by employing addition agents which form low-boiling azeotropes. Benzene may be used as such addition agent. although she! the well known aneotrope-forming substances. e. g. aromatic hydrocarbons. may be used with equal facility. Manifestly, such addition agents must be inert substances and may or may not form low-boiling azeotropic mixtures with the desired reaction product. i. e. the amides or imldes formed. In general, the amides are relatively high-boiling compounds and are recovered'from the reaction vessel without resorting to distillation of these amides or imides.-

They may then be. if desired, purified in any well known manner to separately recover these novel compounds in a pure or substantially pure manner, this recovery and purification being effected by any suitable means such as stratification. extraction, salting out, use of drying agents. and the like, the particular recovery and purification system to be employed depending upon the physical and chemical properties of the particular compound to be treated.

The novel amides may be prepared by reacting a single substituted or unsubstituted suifolanyiamine or sulfolenylamine with a single saturated or unsaturated carboxylic acid or anhydride. Thus, the character of the novel amides maybe controlled by varying the character of the reactants. On the other hand. mixed amides may be prepared by reacting a mixture of difso that only one of the hydrogen atoms attached on the amino radical is substituted by an acyl radical, thus producing a substituted amide. However, it is possible. for example, by employing a polybasic carboxylic acid anhydrlde to effect the reaction under such conditions that both of the hydrogen atoms are substituted by acyl radicals to produce a substituted imide. Also, it is possible to employ a dicarboxylic acid which may be saturated or unsaturated and effect the reaction so as to cause both carboxyl groups to react with the same molecule of the sulfolanylamine or sulfolenylamine.

The following examples are given for the purpose of illustrating certain specific embodiments of the present invention. It is to be understood however that these examples are not to be considered limiting.

Example I into the kettle. During this addition, the temperature varied between about 60 C. and about C. In a short time, a solid white crystailine material separated. This material was removed and re-crystallized from isopropyl alco- 1101. An analysis gave the following results:

The above and other results proved that the reaction product was N-(3-sulfolanyl) acetamide.

Example If Approximately 70 grams (0.25 mol) of oleic acid, about 36 grams (0.25 mol) of 3-sulfolanylamine, and about 100 cc. of benzene were introduced into a still and heated with refluxing to separate the water formed as a byproduct of the reaction. Thereafter, the benzene was distilled .01! by heating to a temperature of about 200 C.

The residual material was then introduced into a flask, and washed with diethyl ether to remove any unreacted oleic acid. The solid residue was then filtered off, washed with hot water to remove any unreacted sulfolanylamine, re-filtered, and finally dried by heating for about 2 hours at a temperature of about 100 C. and a pressure of between about 1 and 2 mm. of mercury. The final product, which was found by analysis to be N-(3-sulfoianyl) oleylamide, is a waxy material, substantially insoluble in kerosane, and having a melting point of about 87 C. to 88 C. It dissolves nitrocellulose and cellulose acetate. It is very stable and shows substantially no decomposition even upon heating to 275 C. at 1 mm. of mercury pressure.

Example III About 282 grams (1 moi) of oleic acid, 144

grams (1 equivalent weight) of 95% pure 3-su1- iolanylamine and 100 cc. of benzene were introduced into a one-liter flask connected to a separating head. The mixture was then heated with reflux for about 12 hours. The water formed as a by-product was removed from the system during this heating step. The remaining reaction product was washed with diethyl ether to remove any unreacted oleic acid, then with hot water to remove any unreacted sulfolanylamine, and then pumped to dryness for a period of about 36 hours at a temperature of about 100 C. The

waxy product thus obtained had a melting point of between about 87 C. and 88 C., was stable even when heated to boiling (approximately 350 C.), and wasfound by analysis to be N-(3-sultolanyl) oleylamide.

Example IV Carbon per eent 40.19

Hydrogen do 6.27

Sulfur do 18.1

Nitrogen do 7.66

Melting Point C 150-152 Yield "per cent 78 The novel amides and imides find utility in a 6 the amino group, are waxy in character, and may be used as ingredients in the manufacture of varnishes, lacquers, floor polishes, furniture polishes, automobile polishes, and the like. Also,

these novel compounds may be employed in paints as protective means, e. g. for the protection of various apparatuses from corrosive fumes, salt water, etc. At least some of the amides and imides are also highly suitable as plasticizers and tackifiers in natural and synthetic resins, e. g. cellulose acetate, polyvinyl chloride, ethyl cellulose, and the like. They are particularly suitable for plasticizing synthetic fibers prepared from po y-amides, such as the poly-amide prepared from adipic acid and hexamethylenediamine. Other amides are of value as addition compounds to insecticides, the amides having the property of enhancing the action of the usual insecticides of the type of pyrethrum. The novel compounds may also be sulfated to form excellent detergents. Also, the novel amides and imides, and particularly those having unsaturated acyl radicals, may be sulfurized to produce highly desirable substances which may be used as addition agents in lubricating oils and grease to reduce corrosive and/or abrasive wear, scuflin etc.

We claim as our invention:

1. N-(3-sulfolany1) acetamide of the formula:

cH,oH-NH( 1-cm J Hi z 2% O O 2. N-(3-sulfolanyl) oleylamide of the formula:

3. N-(3-sulfolanyl) Z-e'thyl-hexoylamide of the formula:

wherein R is the acyl radical of an unsaturated fatty acid.

5. An N-(3-sulfolanyi) amide of a saturated fatty acid of the formula:

wherein R is the acyl radical of a saturated fatty acid.

6. An amide of a sulfolanylamine and a monocarboxylic acid. wherein the amide nitrogen atom is directly attached to the acyl radical of said acid and to a nuclear carbon atom in said sulfoianyla- 7 8 mine at least once removed from the nuclear 3111- REFERENCES CITED fur 8mm therein. 1 1 n I 7. An amide of a sulfolanylamine and a car- 5 5 3 gggg ces record m boxyllc acid, wherein the amide nitrogen atom is 1 directly attached! the ac!!! radical 01' said acid 5 UN TE STATES PATENTS and to a nuclear carbon atom insaid eulrolanyb' Number Name I Date amine.

w. RUPERT C. MORRIS. OTHER REFERENCES EDWARD SHOKAL- 10 Chemical Abstracts, vol. 27, 2443 (1933). 

